CN102093605B - Tire rubber composition and pneumatic tire - Google Patents

Abstract

It is an object of the present invention to provide a tire rubber composition excellent in performances such as silica dispersibility and processability. The present invention relates to a tire rubber composition, comprising: a rubber component that contains an epoxidized natural rubber; silica; and a silane coupling agent, wherein the amount of the epoxidized natural rubber in 100% by mass of the rubber component is 15% by mass or more, the silica has a CTAB specific surface area of 180 m 2 /g or more and a BET specific surface area of 185 m 2 /g or more, and the silane coupling agent contains a mercapto group.

Description

Rubber composition for tire and pneumatic tyre

Technical field

The present invention relates to a kind of rubber composition for tire and a kind of pneumatic tyre that uses this rubber combination to produce.

Background technology

In recent years, consider the exhaustion of petroleum resources, reduction of rolling resistance, environment etc., people provide contain rubber for example natural rubber as the rubber composition for tire tread of main ingredient (for example, referring to,, patent documentation 1).Yet, for example, with the tyre surface (tread) of the main rubber components of natural rubber (NR) conduct, by the problem of rubber combination, be than the tyre surface with rubber such as styrene-butadiene rubber(SBR) (SBR), to use conventional rubber composition poor on wet earth-catching property.Therefore, in order to improve wet earth-catching property, epoxy natural rubber (ENR) has been used to tire tread, and has therefore actively solved petroleum resources exhaustion and reduced CO ₂the problem of discharge.

Therefore, the use of ENR provides the tyre surface (tread) with good wet earth-catching property to use rubber combination.Yet if rubber combination is used in particular for high-performance (ultralow section) tire and for the tire of the traction engine of passenger car, compares with conventional rubber composition with the tyre surface that contains SBR, this rubber combination requires further improvement in wear resistance.

At tyre surface (tread), use in rubber combination, because fuel economy and wet earth-catching property are compatible, therefore use silicon-dioxide as reinforced filling.Yet, in the rubber components of the ENR more than containing predetermined amount, be difficult to dispersed silicon dioxide, particularly white rouge (finely-divided silica) well.At aspects such as silicon-dioxide dispersibilitys, in the rubber combination that silane coupling agent is generally used for containing silicon-dioxide.The silane coupling agent that contains sulfydryl is highly active and has high-performance, but has very short time of scorch.Therefore, in tire industry, be difficult to the actual silane coupling agent that contains sulfydryl that uses.

Meanwhile, contain as the carbon black of reinforced filling and be generally used for sidewall and tread base by mixing the rubber combination of the rubber components of following rubber acquisition: demonstrating the NR of outstanding tensile strength and tear strength, the rubber such as divinyl rubber (BR) of improvement warp resistance crack growth resistance.Yet, similar to rubber composition for tire tread, recently need the fuel economy of sidewall or rubber composition for base tread.

Therefore, consider with white the filler for example alternative major part of silicon-dioxide or all carbon blacks.Yet, with carbon black comparison, with white filler, substitute and usually can cause the reduction of dispersibility.Therefore, may not fully ensure energy-to-break (tensile strength * extension at break), and the problem that therefore causes splitting resistance and warp resistance crack growth resistance to decline.Consider exhaustion and the CO of petroleum resources ₂tightening up of gaseous emission rules, is not only replacement carbon black, it is desirable to the rubber that is derived from non-oil resource for example ENR replace for example BR of synthetic rubber, to increase the use per-cent of non-oil resource in tire.

In order to meet these needs, patent documentation 2 and 3 discloses a kind of sidewall rubber combination, and it comprises silicon-dioxide and NR and ENR, to increase the content of non-oil resource, and it has good warp resistance crack growth resistance and tear strength.Yet the performances such as the splitting resistance of this rubber combination, warp resistance crack growth resistance still need to improve, particularly in the situation for high-performance tire.

Patent documentation 1:JP 2003-64222A

Patent documentation 2:JP 2006-70093A

Patent documentation 3:JP 2007-56205A

Summary of the invention

It is a kind of at performance for example silicon-dioxide dispersibility and the outstanding rubber composition for tire of processibility, to address the above problem that the object of the invention is to provide.More particularly, the object of the invention is to provide: a kind of rubber composition for tire tread, wherein good rolling resistance and wear resistance highly compatible, and its wet earth-catching property and dry earth-catching property outstanding; And a kind of rubber combination for sidewall or tread base, it has improved rolling resistance, splitting resistance and warp resistance crack growth resistance in a kind of well balanced mode.The present invention also aims to provide a kind of pneumatic tyre that uses this rubber combination to produce.

The inventor has been found that: trending towards causing in wear resistance, splitting resistance, warp resistance crack growth resistance and silicon-dioxide dispersibility in the rubber combination that contains epoxy natural rubber and silicon-dioxide of problem, having more than particular value CTAB specific surface area and the silicon-dioxide of BET specific surface area more than particular value can provide the good dispersibility of white rouge and good scorching quality with mixing of the silane coupling agent that contains sulfydryl simultaneously, and this has caused of the present invention completing.

The present invention relates to a kind of rubber composition for tire, it comprises: the rubber components that contains epoxy natural rubber, silicon-dioxide and silane coupling agent, wherein, in the rubber components of 100 quality %, the content of epoxy natural rubber is that more than 15 quality % silicon-dioxide has 180m ²more than/g CTAB specific surface area and 185m ²bET specific surface area more than/g, and silane coupling agent comprises sulfydryl.

Silicon-dioxide it is desirable to have granule size (aggregate size) more than 30nm.

Silane coupling agent it is desirable to a kind of multipolymer that contains unit B shown in unit A shown in general formula (1) and general formula (2), and wherein the ratio of unit B is 1 to 70mol% of unit A and the total molar content of unit B:

Wherein, x and y are respectively more than 1 integers, R ¹represent hydrogen, halogen, have side chain or unbranched C _1-30alkyl or alkylidene group, there are side chain or unbranched C _2-30thiazolinyl or alkenylene, there are side chain or unbranched C _2-30the hydrogen atom of alkynyl or alkynylene or alkyl or alkenyl end is by the group of hydroxyl or carboxyl substituted, R ²represent hydrogen, have side chain or unbranched C _1-30alkyl or alkylidene group, there are side chain or unbranched C _2-30thiazolinyl or alkenylene, there are side chain or unbranched C _2-30alkynyl or alkynylene, and R ¹and R ²can form together ring texture.

This rubber combination it is desirable to for tyre surface, sidewall or tread base.

The invention still further relates to a kind of pneumatic tyre that uses above-mentioned rubber combination to produce.

The epoxy natural rubber that rubber composition for tire according to the present invention comprises specified quantitative, there is more than particular value CTAB specific surface area and the silicon-dioxide of BET specific surface area more than particular value and the silane coupling agent that contains sulfydryl.Therefore, in performance, for example silicon-dioxide dispersibility and processibility are outstanding to this rubber combination.Therefore, if this rubber combination is used to tyre surface (tread), rolling resistance and wear resistance highly compatible so, and can obtain outstanding wet earth-catching property and dry earth-catching property.If this rubber combination, for sidewall or tread base, can well balanced mode improve rolling resistance, splitting resistance and warp resistance crack growth resistance so.In addition, if this rubber combination is used for clinch, so rolling resistance and wear resistance highly compatible.Therefore, if this rubber combination for each tyre assembly, can provide a kind of pneumatic tyre that can well balanced mode obtains these performances.In tire production, this rubber combination also has outstanding processibility (particularly mediating processing characteristics).

Accompanying drawing explanation

Fig. 1 is the view of explanation pore distribution curve.

Embodiment

The epoxy natural rubber that rubber composition for tire of the present invention comprises specified quantitative (ENR), there is more than particular value CTAB specific surface area and the silicon-dioxide of BET specific surface area more than particular value and the silane coupling agent that contains sulfydryl.Because there is this rubber combination of ENR, comprise above-mentioned silicon-dioxide and silane coupling agent, therefore silicon-dioxide disperses well simultaneously.Therefore, low-rolling-resistance can be compatible with good physical strength performances such as () splitting resistance, warp resistance crack growth resistances and wear resistance.In addition, can obtain outstanding wet earth-catching property and dry earth-catching property.Being used in combination of this silicon-dioxide and silane coupling agent can maintain suitable time of scorch and improve scorching quality.Therefore, can prevent rubber incipient scorch, and the processing characteristics of tire production is good.In addition,, because low-rolling-resistance and physical strength and wear resistance are compatible, therefore consider environment, this rubber combination is desirable.

Rubber combination in the present invention comprises ENR.When considering the exhaustion of petroleum resources, reducing rolling resistance and environment, the use of ENR in rubber combination provides good wet earth-catching property, good splitting resistance and warp resistance crack growth resistance is provided and provides for example anti-gas permeability of outstanding performance for air retaining wall for sidewall and tread base for tyre surface (tread).As ENR, can use commercially available ENR, or prepare ENR by epoxidation NR.Method for epoxidation NR is not particularly limited, and its example comprises: chlorohydrination, direct oxidation method, hydrogen peroxide method, alkyl peroxide method and mistake acid system (referring to JP H04-26617B, JP H02-110182A, English Patent GB2113692 etc.).The example of crossing acid system comprises and causes for example method of the reaction between peracetic acid or peroxyformic acid of NR and organic peracid.

More than the epoxy content of ENR it is desirable to 3mol%, more preferably more than 5mol%, more than further it is desirable to 10mol%, and more than it would be desirable 15mol%.If the epoxy content of ENR lower than 3mol%, is difficult to fully improve for example wet earth-catching property of above-mentioned desired properties so.The epoxy content of ENR it is desirable to below 80mol%, more preferably below 60mol%, and further it is desirable to below 40mol%.If the epoxy content of ENR surpasses 80mol%, polymkeric substance trends towards gelation so.

Epoxy content refers to the total ratio to the two keys in natural rubber before epoxidation by the double key number order between epoxidised carbon-to-carbon.Epoxy content for example passes through, and the analytical methods such as volumetry, nucleus magnetic resonance (NMR) analytical method are measured.

The example for the treatment of epoxidised NR comprises those NR that are generally used for rubber industry, for example RSS#3 and TSR20 and latex thereof (latexes).The example of ENR comprises ENR25 and ENR50 (being respectively MRB (Malaysia) produces).These ENR can be used separately, also can be used in combination.

In rubber combination of the present invention, in the rubber components of 100 quality %, the content of ENR is more than 15 quality %.If content lower than 15 quality %, is difficult to improve the wet earth-catching property of rubber combination for tyre surface (tread) so; Be difficult to improve splitting resistance and the warp resistance crack growth resistance of sidewall or rubber composition for base tread; And the performance that is difficult to improve rubber composition for inner liner is anti-gas permeability for example.The upper limit amount of ENR is not particularly limited, and can be 100 quality %.

Particularly in the situation that rubber combination is used for tyre surface, in the rubber components of 100 quality %, the amount of ENR is more than 15 quality %, more than it is desirable to 25 quality %, more preferably more than 30 quality %, and more than further it is desirable to 35 quality %, particularly desirably more than 60 quality %, and more than it would be desirable 85 quality %.In the rubber components of 100 quality %, the upper limit amount of ENR is not particularly limited, and can be 100 quality %, below 95 quality %, or below 90 quality %.

In the situation that rubber combination is used for sidewall or tread base, in the rubber components of 100 quality %, the amount of ENR is more than 15 quality %, more than it is desirable to 20 quality %, more preferably more than 25 quality %, more than further it is desirable to 30 quality %, and particularly desirably more than 35 quality %.In the rubber components of 100 quality %, the content of ENR it is desirable to below 85 quality %, more preferably, below 60 quality %, further it is desirable to 50 quality % or following, and particularly desirably below 45 quality %.If content surpasses 85 quality %, so rolling resistance trend towards higher, and ENR unlikely with other rubber natural rubber formation island structure for example, in fact this may cause the decline of warp resistance crack growth resistance.

In the present invention, rubber components can comprise BR.Thus, can obtain good wear resistance and splitting resistance.In addition, can further improve rolling resistance.If the rubber combination with BR is tyre surface or the sidewall with tire for the heavy-duty vehicle of particularly high-performance (ultralow section) tire and passenger car especially, present better wear resistance and splitting resistance.

BR it is desirable to have cis-contents more than 80 quality %.When for tyre surface, this BR can give better wear resistance.Cis-content is more preferably more than 85 quality %, more than further it is desirable to 90 quality %, and more than it would be desirable 95 quality %.

In addition 5% toluene solution that, it is desirable to BR is 25 ℃ of viscosity of locating to have more than 80cps.Viscosity more than 80cps can significantly be improved processing characteristics and wear resistance.The viscosity of the toluene solution of BR it is desirable to below 200cps.If viscosity surpasses 200cps, viscosity may be too high so, and reduce processing characteristics, and BR is unlikely and other rubber mix.The lower limit of the viscosity of the toluene solution of BR is 110cps more preferably, and more preferably 150cps of its upper limit.

In order to improve wear resistance, can use the BR with 3.0 following molecular weight distribution (Mw/Mn).In addition,, in order to improve processing characteristics and wear resistance simultaneously, can use the BR of the Mw/Mn with 3.0 to 3.4.

In the situation that rubber combination of the present invention comprises BR, in the rubber components of 100 quality %, more than the amount of BR it is desirable to 5 quality %, more preferably more than 10 quality %, and more than further it is desirable to 15 quality %.If its amount is lower than 5 quality %, the effect of the above-mentioned BR that is difficult to so to provide enough.In the rubber components of 100 quality %, the content of BR it is desirable to below 85 quality %, more preferably below 65 quality %, and further it is desirable to below 40 quality %.If its amount surpasses 85 quality %, may reduce processing characteristics so.In addition, the relative proportion of ENR is less, unlikely improves the performances such as wet earth-catching property, anti-gas permeability.

In order to reduce carrying capacity of environment, BR it is desirable to be synthesized by biomass-derived material.For example, can produce by the following method this BR: catalyzer reacts with bio-ethanol, thereby produce divinyl, and as raw material, synthesize BR by divinyl.Although the part that this BR by biomass-derived material synthesized can be used as BR component is mixed, in rubber combination, BR component particularly desirably comprises the biomass-derived BR of 100 quality %.Biomass-derived material refers to " the biogenic renewable organic resources except petroleum resources ".Whether described material is biomass-derived passes through ¹⁴c content determination (ASTM-D6866) checks.

Rubber combination of the present invention can comprise NR as rubber components, and especially when it is during for sidewall and tread base, it is desirable to comprise NR.The example of NR comprises those NR that conventionally use in rubber industry, for example above-mentioned RSS#3 and TSR20.

Especially in the situation that rubber combination is used for sidewall and tread base, in the rubber components of 100 quality %, more than the amount of NR it is desirable to 15 quality %, more preferably more than 40 quality %, more than further it is desirable to 50 quality %, and particularly desirably more than 55 quality %.If its content is lower than 15 quality %, so NR unlikely with ENR formation island structure, this may cause the decline of warp resistance crack growth resistance.In addition, physical strength may decline.In the rubber components of 100 quality %, NR content it is desirable to below 85 quality %, more preferably, below 75 quality %, further it is desirable to 70 quality % or following, and particularly desirably below 65 quality %.If the amount of NR surpasses 85 quality %, the amount of ENR is too small so, and NR is unlikely and ENR forms island structure, and this may cause the decline of warp resistance crack growth resistance.

Except ENR, BR and NR, rubber components also can comprise the rubber such as synthetic polyisoprene (IR), styrene-butadiene rubber(SBR) (SBR), styrene isoprene butadiene rubber (SIBR) (SIBR), ethylene-propylene-elastoprene (EPDM), chloroprene rubber (CR), paracril (NBR).

Rubber combination of the present invention comprises and has 180m ²more than/g CTAB specific surface area and 185m ²the silicon-dioxide of the above BET specific surface area of/g (being also called as hereinafter, " white rouge ").If this white rouge is dispersed in rubber well, can obtain so outstanding physical strength performances such as () splitting resistance, warp resistance crack growth resistances, outstanding dynamic strength (dynamic strength) (energy-to-break), wear resistance, wet earth-catching property and dry earth-catching property, and reduce rolling resistance.

The CTAB of white rouge (cetrimonium bromide) specific surface area it is desirable to 190m ²more than/g, more preferably 195m ²more than/g, and further it is desirable to 197m ²more than/g.If CTAB specific surface area is lower than 180m ²/ g, may not fully improve physical strength and wear resistance so.CTAB specific surface area it is desirable to 600m ²below/g, more preferably 300m ²below/g, and further it is desirable to 250m ²below/g.If CTAB specific surface area surpasses 600m ²/ g, so due to inferior dispersibility, silicon-dioxide may lump, and therefore physicals trends towards declining.

According to ASTM D3765-92, measure CTAB specific surface area.

The BET specific surface area of white rouge it is desirable to 190m ²more than/g, more preferably 195m ²more than/g, and further it is desirable to 210m ²more than/g.If BET specific surface area is lower than 185m ²/ g, may not fully improve so physical strength and wear resistance.

BET specific surface area it is desirable to 600m ²below/g, more preferably 300m ²below/g, and further it is desirable to 260m ²below/g.If BET specific surface area surpasses 600m ²/ g, so due to inferior dispersibility, silicon-dioxide may lump, and therefore physicals trends towards declining.

According to ASTM D3037-81, can measure the BET specific surface area of silicon-dioxide.

More than the granule of white rouge is of a size of 30nm, more than it is desirable to 35nm, more preferably more than 40nm, more than further it is desirable to 45nm, particularly desirably more than 50nm, more particularly desirably more than 55nm, and more than it would be desirable 60nm.Its size it is desirable to below 100nm, more preferably, below 80nm, further it is desirable to below 70nm, and particularly desirably below 65nm.If white rouge has the granule size within the scope of this, this white rouge can disperse well so, can obtain outstanding reinforcement and energy-to-break simultaneously.In addition, can obtain good wear resistance, splitting resistance and warp resistance crack growth resistance.

Granule size is also referred to as granule diameter (aggregate diameter) or highest frequency Stocks equivalent diameter (maximum frequency Stokes equivalent diameter), and refers to the size in following situation: wherein the formed silica agglomerate of reunion by a large amount of primary particles (primary particles) is considered to a particle.For example, a size can be used for example BI-XDC (production of Brookhaven Instruments company) mensuration of disk centrifugal sedimentation particle size analyzing device.

More particularly, a size can by the following method, be measured with BI-XDC.

The deionized water of the silicon-dioxide of 3.2g and 40mL is added in the tall form beaker of 50mL, and the beaker that comprises silica suspension is placed in the crystallizer (crystallizer) that is full of ice.In beaker, with ultrasonic probe (1500-W1.9-cm VIBRACELL ultrasonic probe (Bioblock produces, and uses under 60% maximum power supply output)) by this suspension deagglomeration (deagglomerated) 8 minutes, thereby prepare sample.The sample of 15mL is poured in dish, stirred, and measure under the following conditions: fixed mode, 120 minute analysis time and 2.1 density.

In the register of said apparatus, diameters and Mode value (derivative of accumulation granulometric curve (cumulative granulometric curve) has provided frequency curve, and the peaked X-coordinate in this frequency curve is called as " Mode ") through 16 quality %, 50 quality % (or intermediate value) and 84 quality % have been recorded.

By disk centrifugal sedimentation grain size analysis method, after silicon-dioxide is dispersed in water by ultrasonic deagglomeration, can measure (quality) median size of particle (that is, granule), it is marked as D _w.After analyzing (precipitating 120 minutes), by particle size analyzing device calculated mass size distribution.By (quality) median size D of following formula count particles _w:

$\log D_w=\underset{1}{\overset{n}{\mathrm{\Σ}}}{m}_i\log D_i/\underset{1}{\overset{n}{\mathrm{\Σ}}}{m}_i$

(in formula, m _iat D _ithe total mass of particle in grade).

The average primary particle diameter of white rouge it is desirable to below 25nm, more preferably, below 22nm, further it is desirable to below 17nm, and particularly desirably below 14nm.The lower limit of average primary particle diameter is not particularly limited, and more than it is desirable to 3nm, more preferably more than 5nm, and more than further it is desirable to 7nm.The white rouge with less average primary particle diameter has above-mentioned size and therefore has the structure similar to carbon black.Therefore, more improved silicon-dioxide dispersibility, this has further improved reinforcement, wear resistance, dynamic strength, splitting resistance and warp resistance crack growth resistance.

The average primary particle diameter of white rouge can be measured by the following method: with transmission or sem observation silicon-dioxide, be determined at the particle diameter of observe in the visual field 400 above silicon-dioxide primary particles, and the average particle diameter of these 400 above primary particles.

The D50 of white rouge it is desirable to below 7.0 μ m, more preferably below 5.5 μ m, and further it is desirable to below 4.5 μ m.If D50 surpasses 7.0 μ m, so silicon-dioxide in fact disperse poorer.More than the D50 of white rouge it is desirable to 2.0 μ m, more preferably more than 2.5 μ m, and more than further it is desirable to 3.0 μ m.If D50 is lower than 2.0 μ m, a size also trends towards littlely so, and white rouge unlikely fully disperses.

D50 is the median diameter of white rouge as used herein, and wherein the particle of 50 quality % is less than it.

In white rouge, the ratio of the white rouge that particle diameter ratio 18 μ m are large it is desirable to below 6 quality %, more preferably below 4 quality %, and further it is desirable to below 1.5 quality %.Thus, this silicon-dioxide disperses well, and can obtain desired performance.

Can measure by the following method the D50 and the ratio with the silicon-dioxide of specified particle diameter of white rouge.

By the silica suspension to before ultrasonic deagglomeration, carry out the reunion that granule is estimated in particle size measurement (passing through laser diffraction).In this method, can measure the ability (aptitude) (deagglomeration of the silica dioxide granule of 0.1 to tens micron) for silicon-dioxide deagglomeration.With the VIBRACELL sonic generator (600W, Bioblock produces, and uses) that 19mm diameter probe is housed, carry out ultrasonic deagglomeration under 80% maximum power supply output.By the laser diffraction on MALVERN Mastersizer 2000 particle-size analyzers, carry out particle size measurement.

More particularly, measure by the following method.

At medicine box (pill box) (highly: 6cm, diameter: the silicon-dioxide that takes 1g 4cm), to it, add deionized water to 50g, and the aqueous suspension (this suspension is homogenized by 2 minutes magnetic agitation) that preparation contains 2% silicon-dioxide thus.Carry out subsequently 420 seconds ultrasonic deagglomeration, all suspension homogenizing is poured in the container of particle-size analyzer, carry out subsequently particle size measurement.

The Tile Width W of the pore volume of white rouge (pore volume) it is desirable to more than 0.7, more preferably more than 1.0, further it is desirable to more than 1.3, and particularly desirably more than 1.5.Pore distribution width W it is desirable to below 5.0, more preferably, below 4.0, further it is desirable to below 3.0, and particularly desirably below 2.0.This wider pore distribution causes the improvement of silicon-dioxide dispersibility, and the performance of expectation is provided.

The Tile Width W of the pore volume of silicon-dioxide can measure by the following method.

The pore volume of white rouge can be passed through mercury porosimetry (mercury porosimetry) and measure.Silica sample prebake 2 hours in 200 ℃ of baking ovens.Subsequently, in 5 minutes at sample from baking oven takes out, sample is put into test chamber, and degassed under vacuum.With the surface tension γ of the contact angles of 140 ° and 484dynes/cm (or N/m), pass through Washburn ' s formula calculated hole diameters (AUTOPORE III 9420, powder technology porosity meter).

The pore distribution curve of function that can be by the expression aperture (nm) shown in Fig. 1 and pore volume (mL/g) is measured pore distribution width W.More particularly, record provides the diameter Xs (nm) of pore volume peak value Ys (mL/g), draws the straight line of Y=Ys/2, and the place then intersecting at this straight line and pore distribution curve obtains some a and b.When the X-coordinate (nm) of an a and b is respectively Xa and Xb (Xa > Xb), pore distribution width W equals (Xa-Xb)/Xs.

In the pore distribution curve of white rouge, more than the diameter Xs (nm) that provides pore volume peak value Ys it is desirable to 10nm, more preferably more than 15nm, more than further it is desirable to 18nm, and particularly desirably more than 20nm.Diameter Xs it is desirable to below 60nm, more preferably, below 35nm, further it is desirable to below 28nm, and particularly desirably below 25nm.Diameter Xs within the scope of this can be provided in white rouge outstanding in dispersibility and reinforcement.

In rubber combination of the present invention, the rubber components based on 100 mass parts, more than the content of white rouge it is desirable to 5 mass parts, more preferably more than 10 mass parts, and more than further it is desirable to 15 mass parts.If content lower than 5 mass parts, trends towards obtaining enough reinforcement, physical strength and wear resistance so.Rubber components based on 100 mass parts, what the content of white rouge was desirable is below 150 mass parts, is more desirably below 100 mass parts, and further it is desirable to below 80 mass parts.If content surpasses 150 mass parts, processibility may decline so, and unlikely guarantees good dispersibility.

Particularly in the situation that rubber combination is used for tyre surface (tread), based on 100 mass parts rubber components, more than the content of white rouge it is desirable to 20 mass parts, more preferably more than 40 mass parts, and more than further it is desirable to 50 mass parts.Based on 100 mass parts rubber components, what the content of white rouge was desirable is below 120 mass parts, is more desirably below 95 mass parts, and further it is desirable to below 75 mass parts.If content is lower than lower limit or surpass the upper limit, can present so with above-mentioned with regard to the identical tendency of the tendency described in white rouge content.

In the situation that rubber combination is used for sidewall and tread base, based on 100 mass parts rubber components, more than the content of white rouge it is desirable to 10 mass parts, more preferably more than 20 mass parts, and more than further it is desirable to 25 mass parts.Based on 100 mass parts rubber components, what the content of white rouge was desirable is below 80 mass parts, is more desirably below 50 mass parts, and further it is desirable to below 40 mass parts.If content is lower than lower limit or surpass the upper limit, can present so with above-mentioned with regard to the identical tendency of the tendency described in white rouge content.

Except white rouge, rubber combination of the present invention also can comprise silicon-dioxide.In the case, the rubber components based on 100 mass parts, more than the total amount of silicon-dioxide it is desirable to 15 mass parts, more preferably more than 25 mass parts, and more than further it is desirable to 45 mass parts.Rubber components based on 100 mass parts, total content it is desirable to below 200 mass parts, more preferably below 150 mass parts, and further it is desirable to below 100 mass parts.If this content is lower than lower limit or surpass the upper limit, can present so with above-mentioned with regard to the identical tendency of the tendency described in white rouge content.

Rubber combination of the present invention comprises the silane coupling agent that contains sulfydryl.If the silane coupling agent that is used in combination white rouge and contains sulfydryl in trending towards causing the rubber combination that contains ENR and silicon-dioxide of the performance issues such as silicon-dioxide dispersibility, wear resistance, splitting resistance, warp resistance crack growth resistance, white rouge trends towards slowing down vulcanization rate so.Therefore, although the silane coupling agent that comprises sulfydryl is used, but still can guarantee suitable time of scorch, and obtain good processibility.In addition, this is used in combination and can makes the white rouge with high reinforcement disperse equably in ENR.Therefore, can obtain outstanding reinforcement and energy-to-break and good fuel economy, wear resistance, splitting resistance and warp resistance crack growth resistance.

The silane coupling agent that contains sulfydryl is not particularly limited, and its example comprises 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 2-mercaptoethyl Trimethoxy silane and 2-mercaptoethyl triethoxyl silane.

In these, what be applicable to use is as the silane coupling agent that contains the multipolymer of unit B shown in unit A shown in general formula (1) and general formula (2), wherein the ratio of unit B be unit A and unit B total molar content 1 to 70mol%.

In general formula (1) and general formula (2), x and y are respectively more than 1 integers; R ¹represent hydrogen, halogen, have side chain or unbranched C _1-30alkyl or alkylidene group, there are side chain or unbranched C _2-30thiazolinyl or alkenylene, there are side chain or unbranched C _2-30alkynyl or alkynylene or alkyl or alkylidene group end hydrogen atom are by the group of hydroxyl or carboxyl substituted; R ²represent hydrogen, have side chain or unbranched C _1-30alkyl or alkylidene group, there are side chain or unbranched C _2-30thiazolinyl or alkenylene, there are side chain or unbranched C _2-30alkynyl or alkynylene, and R ¹and R ²can form together ring structure.

The silane coupling agent that contains sulfydryl is highly active, and has significantly improved silicon-dioxide dispersibility.Yet silane coupling agent has the short defect of time of scorch, and rubber combination probably completes incipient scorch when mediating and extruding.Equally, in order to suppress reversion, ENR or NR usually vulcanize together with a large amount of vulcanization accelerators, therefore be difficult to use the silane coupling agent that contains sulfydryl.

On the contrary, in having the silane coupling agent of said structure, the mol ratio of unit A and unit B meets above-mentioned condition.Therefore, with polysulfide silanes for example two (3-triethoxysilylpropyltetrasulfide) tetrasulfide compare, this silane coupling agent can suppress the increase of viscosity between processing period.The chances are for this due to following reason: because the sulfide of unit A is partly C-S-C key, compare with tetrasulfide or disulphide, described sulfide is partly heat-staple.Therefore, the increase of mooney viscosity is less.

When the mol ratio of unit A and unit B meets above-mentioned condition, with hydrosulphonyl silane for example 3-sulfydryl propyl trimethoxy silicane compare, this silane coupling agent can suppress the minimizing of time of scorch.The chances are for this due to following reason: unit B has hydrosulphonyl silane structure, and unit B-SH group by unit A-C ₇h ₁₅part covers.Therefore ,-SH group unlikely and polymer reaction.Therefore, unlikely reduce time of scorch, and unlikely increase viscosity.

For R ¹, the example of halogen atom comprises: chlorine, bromine and fluorine.

For R ¹and R ², have side chain or unbranched C _1-30the example of alkyl comprises: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, 2-ethylhexyl, octyl group, nonyl and decyl.The carbonatoms of alkyl it is desirable to 1 to 12.

For R ¹and R ², have side chain or unbranched C _1-30the example of alkylidene group comprises: ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl and sub-undecyl, sub-dodecyl, sub-tridecyl and sub-tetradecyl, sub-pentadecyl, sub-hexadecyl, sub-heptadecyl and sub-octadecyl.The carbonatoms of alkylidene group it is desirable to 1 to 12.

For R ¹and R ², have side chain or unbranched C _2-30the example of thiazolinyl comprises: vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 1-pentenyl, pentenyl, 1-hexenyl, 2-hexenyl and 1-octenyl.The carbonatoms of thiazolinyl it is desirable to 2 to 12.

For R ¹and R ², have side chain or unbranched C _2-30the example of alkenylene comprises: vinylidene, 1-propenylidene, 2-propenylidene, 1-crotonylidene, 2-crotonylidene, 1-inferior pentenyl, 2-inferior pentenyl, the sub-hexenyl of 1-, the sub-hexenyl of 2-and the sub-octenyl of 1-.The carbonatoms of alkenylene it is desirable to 2 to 12.

For R ¹and R ², have side chain or unbranched C _2-30the example of alkynyl comprises: ethynyl, proyl, butynyl, pentynyl, hexin base, heptyne base, octyne base, n-heptylacetylene base, decynyl, undecyne base and dodecyne base.The carbonatoms of alkynyl it is desirable to 2 to 12.

For R ¹and R ², have side chain or unbranched C _2-30the example of alkynylene comprises: ethynylene, sub-proyl, butynelene, sub-pentynyl, sub-hexin base, sub-heptyne base, sub-octyne base, sub-n-heptylacetylene base, sub-decynyl, sub-undecyne base and sub-dodecyne base.The carbonatoms of alkynylene it is desirable to 2 to 12.

In having the silane coupling agent of said structure, the repetition total degree (x+y) of the multiplicity (y) of the multiplicity of unit A (x) and unit B it is desirable to 3 to 300.If total degree within the scope of this, so unit A-C ₇h ₁₅covered the hydrosulphonyl silane of unit B.Therefore, the minimizing of time of scorch can be suppressed, and the good reactivity of silicon-dioxide and rubber components can be ensured simultaneously.

The example with the silane coupling agent of said structure comprises NXT-Z30, NXT-Z45 and NXT-Z60 (all being produced by Momentive Performance Materials company).These can use separately, also can be used in combination.

White rouge based on 100 mass parts, more than the content of the silane coupling agent that contains sulfydryl it is desirable to 0.5 mass parts, more preferably more than 1.5 mass parts, more than further it is desirable to 2.5 mass parts, and more than it would be desirable 3.5 mass parts.If content is lower than 0.5 mass parts, the unlikely good distribution of white rouge so.Based on 100 mass parts white rouges, what the content of the silane coupling agent that contains sulfydryl was desirable is below 20 mass parts, is more desirably below 15 mass parts, further it is desirable to below 10 mass parts, and it would be desirable below 5 mass parts.If content surpasses 20 mass parts, the dispersiveness of white rouge trends towards with increasing amount, not being improved so, and cost trends towards unnecessarily increasing.In addition, time of scorch trends towards reducing, and the processibility of mediating and extruding trends towards declining.

Rubber combination of the present invention can comprise mixture (the Activator 73A that for example, Struktol company produces) and/or the C of aliphatic carboxylic acid zinc salt and aromatic carboxylic acid zinc salt _4-16(it is desirable to C _6-14, more preferably C _6-12, and further it is desirable to C _6-10) aliphatic carboxylic acid zinc salt (the Struktol ZEH (2 ethyl hexanoic acid zinc salt) that for example, Struktol company produces).

These components have delayed sulfuration, time of scorch that may be too short while having improved the silane coupling agent that contains sulfydryl in use, and improved the dispersibility of silicon-dioxide.These components have also been improved the anti-reversion of ENR or NR, can obtain outstanding control stability and wet earth-catching property and good rolling resistance simultaneously.The use of these components has reduced the sulfur-crosslinked of unnecessary sulphur and bad form, and effective and stable cross-linking set is provided, and the rubber combination with the required rigidity of control stability is provided.In addition, these components provide at the rubber combination to having flexibility under wet earth-catching property and the required relevant cold condition compared with small deformation of earth-catching property.Therefore, these components provide the have higher earth-catching property tread rubber of (particularly under wet condition).These components also provide such tread rubber: this tread rubber is due to the unnecessary sulphur of small amount and bad form is sulfur-crosslinked has good rolling resistance and wear resistance, and its weather resistance is outstanding, to such an extent as to performance can not change much during use.In addition, these components provide sidewall rubber and the tread base rubber with outstanding rolling resistance and weather resistance.

The example of the aliphatic carboxylic acid of the aliphatic carboxylic acid zinc salt in mixture comprises the aliphatic carboxylic acid that is derived from following vegetables oil: for example Oleum Cocois, palm-kernel oil, tea oil, sweet oil, Prunus amygdalus oil, mustard caul-fat, peanut oil, Rice pollard oil, theobroma oil, plam oil, soya-bean oil, Oleum Gossypii semen, sesame oil, Semen Lini oil, Viscotrol C and rapeseed oil; Be derived from for example aliphatic carboxylic acid of butter of animal oil; And the aliphatic carboxylic acid being synthesized by petroleum chemistry etc.Because it is environmentally friendly, so it is desirable to the aliphatic carboxylic acid of plant-derived oil, and be more preferably derived from the aliphatic carboxylic acid of Oleum Cocois, palm-kernel oil or Oleum Cocois, thereby prepare for the minimizing of following oil supply, and fully suppress reversion.

In mixture, the carbonatoms in aliphatic carboxylic acid it is desirable to more than 4, and more preferably more than 6.If the carbonatoms in aliphatic carboxylic acid is less than 4, dispersibility trends towards declining so.The carbonatoms of aliphatic carboxylic acid it is desirable to below 16, more preferably, below 14, further it is desirable to below 12.If the carbonatoms in aliphatic carboxylic acid surpasses 16, trend towards so fully not suppressing reversion.

Herein, the aliphatic group in aliphatic carboxylic acid can be a group with chain structure, alkyl for example, or group with ring structure cycloalkyl for example.

The example of the aromatic carboxylic acid in the aromatic carboxylic acid zinc salt in mixture comprises phenylformic acid, phthalic acid, mellitic acid, hemimellitic acid, trimellitic acid, diphenic acid, toluic acid and naphthoic acid.In these, because can fully suppress reversion, it is desirable to phenylformic acid, phthalic acid or naphthoic acid.

Aliphatic carboxylic acid zinc salt in mixture and the content between aromatic carboxylic acid zinc salt are than (mol ratio: (aliphatic carboxylic acid zinc salt)/(aromatic carboxylic acid zinc salt), hereinafter to be referred as " content ratio ") it is desirable to more than 1/20, more preferably more than 1/15, and further it is desirable to more than 1/10.If content than lower than 1/20, can not be so eco-friendly and can not for future oil supply minimizing ready, and the dispersibility of mixture and stability trend decline.In addition, content ratio it is desirable to below 20/1, more preferably, below 15/1, further it is desirable to below 10/1.If content than surpassing 20/1, trends towards fully not suppressing reversion so.

More than zinc content in mixture it is desirable to 3 quality %, more preferably more than 5 quality %.If the zinc content in mixture lower than 3 quality %, trends towards fully not suppressing reversion so.In addition, the zinc content in mixture it is desirable to below 30 quality %, more preferably below 25 quality %.If the zinc content in mixture surpasses 30 quality %, trend towards so reducing processibility and trending towards unnecessarily increasing cost.

C _4-16aliphatic carboxylic acid in aliphatic carboxylic acid zinc salt can be straight chain or side chain, and can be to have for example aliphatic carboxylic acid of cycloalkyl of ring structure.This aliphatic carboxylic acid can be saturated fatty acid or unsaturated fatty acids.This aliphatic carboxylic acid can be for example aliphatic dicarboxylic acid or aliphatic tricarboxylic acids of aliphaticpolycarboxylic acid.

C _4-16the example of the aliphatic carboxylic acid in aliphatic carboxylic acid zinc salt comprises that for example butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undeeanoic acid, laurostearic acid, isopropylformic acid, isovaleric acid, PIVALIC ACID CRUDE (25), isocaproic acid, isoamyl acetic acid, isocaprylic acid, sad, the different n-nonanoic acid of dimethyl, isodecyl acid of saturated fatty acid, different undeeanoic acid, different laurostearic acid, 2 Ethylbutanoic acid, 2 ethyl hexanoic acid, 2-butyl are sad, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid and sebacic acid; And unsaturated fatty acids for example butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octylenic acid, nonenoic acid, nonene acyl group, undecylenic acid and lauroleic acid.In these, because it highly suppresses reversion, and industrial abound with and cheaply, therefore particularly desirably 2 ethyl hexanoic acid.These can use separately, also can be used in combination.

Rubber components based on 100 mass parts, C _4-16more than the total content of aliphatic carboxylic acid zinc salt and said mixture it is desirable to 0.2 mass parts, more preferably more than 0.5 mass parts, and more than further it is desirable to 1 mass parts.If total content lower than 0.2 mass parts, can not guarantee so enough anti-reversions and improve the effect of cross-linking density, and therefore trend towards being difficult to reduce rolling resistance and improving control stability etc.Rubber components based on 100 mass parts, total content it is desirable to below 10 mass parts, more preferably below 7 mass parts, and further it is desirable to below 5 mass parts.If total content surpasses 10 mass parts, may occur frosting so, and the improvement effect that increases content may become less, cause cost unnecessarily to increase.

Rubber combination of the present invention can comprise alkaline fat acid metal salt.Alkaline fat acid metal salt has neutralized the synthetic acid for ENR, and can prevent from mediating and the thermal destruction of ENR during sulfuration.In addition, also can suppress reversion.

The example of the metal in alkaline fat acid metal salt comprises sodium, potassium, calcium and barium.In these, consider improve stable on heating higher efficacy and with epoxy natural rubber compared with high-compatibility, it is desirable to calcium and barium.The object lesson of alkaline fat acid metal salt comprises: Metallic stearates is sodium stearate, Magnesium Stearate, calcium stearate and barium stearate for example; And oleic acid metal-salt for example sodium oleate, magnesium oleate, calcium oleate and barium oleate.In these, due to its improve stable on heating higher efficacy, with epoxy natural rubber compared with high-compatibility and relatively low cost, it is desirable to calcium stearate and calcium oleate.

ENR based on 100 mass parts, more than the content of alkaline fat acid metal salt it is desirable to 1 mass parts, more preferably more than 1.5 mass parts, and more than further it is desirable to 3 mass parts.If content, lower than 1 mass parts, so unlikely obtains enough thermotolerance and anti-reversion.ENR based on 100 mass parts, the content of alkaline fat acid metal salt it is desirable to below 10 mass parts, and more preferably below 8 mass parts.If content surpasses 10 mass parts, tensile strength and wear resistance trend towards declining so.

Rubber combination of the present invention can comprise lipid acid for example stearic acid, Palmiticacid, myristic acid, lauric acid, sad, oleic acid and linolic acid.In these, due to its low cost, it is desirable to stearic acid.

In rubber combination of the present invention, based on 100 mass parts rubber components, mixture, the C of alkaline fat acid metal salt, aliphatic carboxylic acid zinc salt and aromatic carboxylic acid zinc salt _4-16more than the total content of aliphatic carboxylic acid and lipid acid it is desirable to 2.5 mass parts, more preferably more than 4 mass parts, more than further it is desirable to 6 mass parts, and particularly desirably more than 7 mass parts.If total content lower than 2.5 mass parts, trends towards fully suppressing degraded and the reversion of ENR so, and trend towards not improving the effectively crosslinked of increase sulphur.Rubber components based on 100 mass parts, the total content of said components it is desirable to below 20 mass parts, more preferably below 17 mass parts, and further it is desirable to below 12 mass parts.If total content surpasses 20 mass parts, rolling resistance trends towards declining, and wear resistance, dynamic strength (energy-to-break) and physical strength (splitting resistance and warp resistance crack growth resistance) may actually decline.

In the situation that rubber combination is used for tyre surface, the rubber components of 100 mass parts of take is benchmark, more than the total content of said components it is desirable to 2.5 mass parts, more preferably more than 4 mass parts, more than further it is desirable to 6 mass parts, and particularly desirably more than 7 mass parts.Rubber components based on 100 mass parts, total content it is desirable to below 20 mass parts, more preferably below 17 mass parts, and further it is desirable to below 12 mass parts.If total content is lower than lower limit or surpass the upper limit, can present so the tendency identical with tendency with regard to described in said components total content.

In the situation that rubber combination is used for sidewall and tread base, based on 100 mass parts rubber components, more than the total content of said components it is desirable to 2.5 mass parts, more preferably more than 3.0 mass parts, and more than further it is desirable to 3.5 mass parts.Rubber components based on 100 mass parts, total content it is desirable to below 20 mass parts, more preferably below 10 mass parts, and further it is desirable to below 8 mass parts.If total content is lower than lower limit or surpass the upper limit, can present so the tendency identical with tendency with regard to described in said components total content.

Except said components, rubber combination optionally comprises the matching component that is usually used in rubber industry.The example of matching component comprises filler for example carbon black, oils or softening agent; Antioxidant; Antiaging agent; Zinc oxide; Vulcanizing agent is sulphur and the compound that contains sulphur for example; And vulcanization accelerator.

By conventional method, prepare rubber combination of the present invention.More particularly, produce by the following method rubber combination: for example, for example Banbury, kneader, mill are mediated said components, the mixture that then sulfuration generates with equipment.This rubber combination can be used for each tyre assembly, and is specially adapted to tyre surface (tread), sidewall and tread base.

As being applicable to the method for rubber combination that preparation comprises NR, ENR and silicon-dioxide, be the method comprising the steps: (I) mediate natural rubber and silicon-dioxide; And (II) mediate epoxy natural rubber.The method is specially adapted to production sidewall or rubber composition for base tread.

In mediating operation (I), consider processibility, the content of NR it is desirable to 40 to 100 quality % of the total content of the NR that uses in all kneading operations, and particularly desirably 100 quality %.In mediating operation (I), consider warp resistance crack growth resistance, the content of silicon-dioxide it is desirable to 80 to 100 quality % of the total content of the silicon-dioxide that uses in all kneading operations, and particularly desirably 100 quality %.In mediating operation (I), can by other chemical reagent, for example tenderizer, antiaging agent, stearic acid and zinc oxide add in rubber combination.

In mediating operation (II), consider warp resistance crack growth resistance, the content of ENR it is desirable to 50 to 100 quality % of the total content of the ENR that uses in all kneading operations, and particularly desirably 100 quality %.Above-mentioned alkaline fat acid metal salt it is desirable to sneak in mediating operation (II).

Pneumatic tyre of the present invention can be produced with above-mentioned rubber combination by conventional method.

More particularly, the unvulcanized rubber composition extrusion processing that comprises above-mentioned composition is become to for example shape of tyre surface, sidewall or tread base of tyre assembly, then on tyre building machine, with ordinary method and other tyre assembly mold pressing to form not vulcanized tyre.Then, incite somebody to action not vulcanized tyre heating and pressurizing in vulcanizing apparatus, thereby make tire.

The airtyred application of using rubber combination of the present invention to produce is not particularly limited, and described pneumatic tyre is specially adapted to the tire as the heavy-duty vehicle in high-performance tire tires such as () high flat tire, racing tires and passenger car.

Embodiment

According to embodiment, the present invention will be described in more detail, but the invention is not restricted to these embodiment.

Hereinafter, for each chemical reagent of embodiment and comparative example, list in as follows.

Epoxy natural rubber 1 (ENR-25): MRB company (Malaysia) produces (epoxy content: 25mol%, Tg:-47 ℃)

Epoxy natural rubber 2 (ENR-37.5): trial product (MRB company (Malaysia) produces, epoxy content: 37.5mol%, Tg:-35 ℃)

BR1: BR 150B (cis-Isosorbide-5-Nitrae-linkage content: 97 quality %, ML that Ube Industries, Ltd produces ₁₊₄(100 ℃): the viscosity of 40,5% toluene solutions at 25 ℃: 48cps, Mw/Mn:3.3)

BR2: trial product BRA (cis-Isosorbide-5-Nitrae-linkage content: 98 quality %, ML that Ube Industries, Ltd produces ₁₊₄(100 ℃): the viscosity of 47,5% toluene solutions at 25 ℃: 122cps, Mw/Mn:3.3)

NR：RSS#3

Zeosil 1115MP (the CTAB specific surface area: 105m that silica 1: Rhodia produces ²/ g, BET specific surface area: 115m ²/ g, average primary particle diameter: 25nm, granule size: 92nm, pore distribution width W: 0.63, provide the diameter Xs:60.3nm at the pore volume peak in pore distribution curve)

Zeosil HRS 1200MP (the CTAB specific surface area: 195m that silicon-dioxide 2:Rhodia produces ²/ g, BET specific surface area: 200m ²/ g, average primary particle diameter: 15nm, granule size: 40nm, D50:6.5 μ m, surpasses the ratio of the particle of 18 μ m in particle diameter: 5.0 quality %, pore distribution width W: 0.40, provide the diameter Xs:18.8nm at the pore volume peak in pore distribution curve)

Zeosil Premium 200MP (the CTAB specific surface area: 200m that silicon-dioxide 2:Rhodia produces ²/ g, BET specific surface area: 220m ²/ g, average primary particle diameter: 10nm, granule size: 65nm, D50:4.2 μ m, particle diameter surpasses the ratio of the particle of 18 μ m: 1.0 quality %, pore distribution width W: 1.57, provide the diameter Xs:21.9nm at the pore volume peak in pore distribution curve)

The Si69 (two (3-triethoxysilylpropyltetrasulfide) tetrasulfide) that silane coupling agent 1:Degussa AG produces

NXT-Z45 (the multipolymer of unit A and unit B (unit A:55mol%, unit B: 45mol%)) that silane coupling agent 2:Momentive Performance Materials company produces

Si363 (the sulfhydryl content: 3.3%) that silane coupling agent 3:Degussa AG produces

Vegetables oil: the refined soybean oil of the Nisshin Oil Mills, Ltd (S) (iodine number: 131, there are 18 fatty acid components of carbon atoms above: 84.9%)

Alkaline fat acid metal salt: the calcium stearate that Japan Oil Co produces

Stearic acid: " KIRI " that Japan Oil Co produces

Anti-reversion agent (mixture of aliphatic carboxylic acid zinc salt and aromatic carboxylic acid zinc salt): Activator73A ((i) aliphatic carboxylic acid zinc salt: the lipid acid (C that is derived from Oleum Cocois that Struktol company produces _8-12) zinc salt, (ii) aromatic carboxylic acid zinc salt: Zinc dibenzoate, mol ratio content: 1/1, zinc content: 17 quality %)

Zinc oxide: No. 2, zinc oxide, Mitsu Mining & Smelting Co., Ltd produces

Antiaging agent: the Nocrac 6C (N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine) that the emerging chemical industry of imperial palace Co., Ltd. produces

Wax 1: the SUNNOC Wax that the emerging chemical industry of imperial palace Co., Ltd. produces

The Ozoace 0355 that wax 2:Nippon Seiro company produces

Sulphur: the sulphur powder that He Jian chemical industry Co., Ltd. produces

Vulcanization accelerator TBBS: the Nocceler NS (the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine) that the emerging chemical industry of imperial palace Co., Ltd. produces

Embodiment 1 to 7 and comparative example 1 to 7

According to each formula as shown in table 1, by 1.7L Banbury, the formula material except sulphur and vulcanization accelerator is mediated 5 minutes, thereby given the drop temperature of 150 ℃, to form kneaded material.In gained kneaded material, add sulphur and vulcanization accelerator, and they are mediated 3 minutes at 80 ℃ by two roller mills, thereby unvulcanized rubber composition is provided.

The unvulcanized rubber composition obtaining press vulcanization 30 minutes at 150 ℃, thus make vulcanized rubber thin slice.

In addition, the unvulcanized rubber composition mill obtaining is pressed as tire tread form, with other tyre assembly combination, then at 150 ℃, vulcanize 30 minutes.Thus, make test tire.

Embodiment 8 to 12 and comparative example 8 to 12

The chemical reagent of content shown in operation in table 21 is mediated 5 minutes with Banbury, thereby given the drop temperature of about 150 ℃.Firm discharging (discharged), just epoxy natural rubber 1 and alkaline fat acid metal salt are joined in the kneaded material forming in operation 1 with content shown in operation 2, and mediate the mixture obtaining, thereby give the drop temperature of about 150 ℃.Subsequently the sulphur of content shown in operation 3 and vulcanization accelerator are sneaked in the mixture obtaining in operation 2, and at 80 ℃, mediate 3 minutes with mill, produce thus unvulcanized rubber composition.

By the unvulcanized rubber composition obtaining press vulcanization 30 minutes at 150 ℃, thereby provide vulcanized rubber thin slice and vulcanized rubber test film.

In addition, the unvulcanized rubber composition mill obtaining is pressed as sidewall shape and tread base shape, with other tyre assembly assembling, then at 150 ℃, vulcanize 30 minutes, thereby test tire is provided.

The unvulcanized rubber composition making, vulcanized rubber thin slice, vulcanized rubber test film and test tire are assessed as follows.Test-results as shown in Table 1 and Table 2.

(1) energy-to-break index

The tensile strength of each vulcanized rubber thin slice and extension at break are measured according to JIS K6251 " mensuration of sulfuration or thermoplastic elastomer-tensile stress-emergent property ".Then, pass through formula: " (tensile strength) * (extension at break)/2 " calculate energy-to-break, and calculate energy-to-break index by following formula.

(energy-to-break index)=(each formula energy-to-break)/(comparative example 1 or 8 energy-to-break) * 100

(2) cut resistance test (wear test)

The test tire making is arranged on car, and after 8000km has been travelled in urban district, measures the minimizing of the degree of depth of study on tire pattern groove at vehicle.Then, calculate the operating range that tyre tread gash depth reduces 1mm.The abrasion resistance index of comparative example 1 is considered to 100, and the minimizing of the degree of depth of the tyre tread groove of each formula is expressed as index by following equation.Abrasion resistance index is larger, and wear resistance is better.

(abrasion resistance index)=(reducing the operating range of 1mm tyre tread gash depth in each formula)/(reducing the operating range of 1mm tyre tread gash depth in comparative example 1) * 100

(3) time of scorch

According to the explanation of JIS K6300, by the physical test method of unvulcanized rubber, carry out Mooney scorch test, be then determined at the t10[minute at 130 ± 0.5 ℃].T10 is expressed as to the index (Mooney scorch time index) with respect to the standard recipe that is considered to 100 (comparative example 1 or 8).If time of scorch is short, there is so the problem that trends towards occurring rubber incipient scorch.In this assessment, if index is below 70, the problem of rubber incipient scorch may for example complete and mediate and extrude middle appearance in operation.

(4) rolling resistance test

Produce vulcanized rubber thin slice (2mm * 130mm * 130mm), and cut out mensuration test film from vulcanized rubber thin slice.Then, with visco-elasticity spectrometer VES (production of Iwamoto Seisakusho company), measure under the following conditions the tan δ of each test film: the temperature of 50 ℃; 10% initial strain; 2% dynamic strain; And the frequency of 10Hz.Comparative example 1 or 8 rolling resistance index are considered to 100, and rolling resistance of each formula is expressed as index by following equation.Rolling resistance index is less, and rolling resistance is less and better.

(rolling resistance index)=[(each formula Tan δ)/(comparative example 1 or 8 Tan δ)] * 100

(5) the dispersed index of silicon-dioxide

Produce vulcanized rubber thin slice (2mm * 130mm * 130mm) as vulcanizate compositions, and cut out mensuration test film from vulcanized rubber thin slice.According to JIS K6812 " method of the dispersity in polyolefin pipe, accessory and compound for assessment of pigment or carbon black ", calculate the number of the silicon-dioxide agglomerate in vulcanizate compositions, and calculate its scatter coefficient (%).The scatter coefficient of standard recipe (comparative example 1 or 8) is considered to 100, and the silicon-dioxide scatter coefficient of each formula is expressed as index by following equation.The dispersed index of silicon-dioxide is larger, and silicon-dioxide disperses better, and silicon-dioxide dispersibility is better.

(silicon-dioxide dispersed index)=[(scatter coefficient of each formula)/(comparative example 1 or 8 scatter coefficient)] * 100

(6) wet earth-catching property

The wet earth-catching property of assessment on the basis of the braking ability obtaining by ABS (Anti-lock Braking System) (ABS) evaluation test.That is, above-mentioned experiment tire is arranged on the passenger car that is equipped with ABS of 1800cc grade, at bituminous pavement (moist pavement state, surface friction coefficient: carry out actual vehicle running experiment about 50), and calculate on moist bituminous pavement the deceleration of vehicle stop required separation distance from 100km/h starts to brake.The wet earth-catching property index of comparative example 1 is considered to 100, and the deceleration of each formula is expressed as wet earth-catching property index by following equation.Wet earth-catching property index is larger, and braking ability is better, and wet earth-catching property is better.

(wet earth-catching property index)=(deceleration of comparative example 1)/(deceleration of each formula) * 100

(7) dry earth-catching property

Test tire is arranged on passenger car, on dried asphalt road in testing ground, carry out actual vehicle test run(s), and assess various performances for example control response (responsiveness), rigidity and earth-catching property according to officer's sensory evaluation.The results of property of each formula is expressed as with respect to comparative example 1 index that is considered to 100 (dry earth-catching property index).Index value is larger, and dry earth-catching property and control stability are better.

(8) tear test

According to JIS K6252 " mensuration of sulfuration or thermoplastic elastomer-tear strength ", use without scarfing right angle experiment slice (vulcanized rubber thin slice) and measure tear strength (N/mm).The tear strength of standard recipe (comparative example 8) is considered to 100, and calculates tear strength index by following equation.Tear strength index is larger, and tear strength is higher and better.

(tear strength index)=(tear strength of each formula)/(tear strength of comparative example 8) * 100

(9) test of deflection crack growth (De Mattia)

According to JIS K6260 " test method (De Mattia) of sulfuration or thermoplastic elastomer deflection crackle and crack growth ", under the relative humidity of the temperature of 23 ℃ and 55%, measure each vulcanized rubber test film sample after 100 ten thousand testing campaign crack length or until the crack growth in each sample to the testing campaign number of 1mm.According to obtained testing campaign number and crack length, by until the crack growth in each sample is expressed as denary logarithm to the deflection cycle number of 1mm, the denary logarithm of comparative example 8 is considered to 100, and denary logarithm of each formula is expressed as index.Herein, 70% and 110% per-cent refers to the elongation with respect to initial vulcanized rubber test film sample separately.Denary logarithm index is larger, and crackle more can not be grown, and warp resistance crack growth resistance is better.

(deflection crack growth (De Mattia) index (70%, 110%))=[(until the crack growth in each formula is to denary logarithm of the deflection cycle number of 1mm)/(until the crack growth in comparative example 8 is to denary logarithm of the deflection cycle number of 1mm)] * 100

(10) constant elongation fatigue test (constant stretching fatigue test)

With No. three dumbbells, under the following conditions each vulcanized rubber thin slice is carried out the recirculation strained tensile test of uniform amplitude (constant amplitude): 50% maximum strain and the frequency of 5Hz, and do not form in advance initial crack.After repeating 500 ten thousand circulations of this test, broken vulcanized rubber thin slice is evaluated as " C ", has the vulcanized rubber thin slice that splits literary composition or damage to be evaluated as " B ", and complete vulcanized rubber thin slice is evaluated as " A ".

[table 1]

Rubber composition for tire tread

In comparative example 1, the silicon-dioxide of use is not according to white rouge of the present invention, and has used the coupling agent that there is no sulfydryl.Therefore, poor than embodiment of the energy-to-break of comparative example 1 and wear resistance.In comparative example 2, used white rouge, but do not used the coupling agent that contains sulfydryl.Therefore, in comparative example 2, silicon-dioxide disperses bad, and energy-to-break is lower than the energy-to-break of embodiment, and wear resistance is equal to or less than the wear resistance of embodiment.In addition poor than embodiment of the wet earth-catching property of comparative example 2.In comparative example 3, used white rouge, but there is no to use the coupling agent that contains sulfydryl.Therefore, in comparative example 3, silicon-dioxide disperses non-constant, and energy-to-break, wear resistance and wet earth-catching property are on duty mutually.

In comparative example 4, the coupling agent that has used conventional silicon-dioxide rather than white rouge and contained sulfydryl.Therefore, burn the time shorter.Because do not use white rouge in comparative example 4, so poor than embodiment of energy-to-break and wear resistance.In comparative example 5, used conventional silicon-dioxide rather than white rouge and be different from the coupling agent that contains sulfydryl in comparative example 4.Therefore, time of scorch is very short, and is difficult to process by common method.In addition, the energy-to-break of comparative example 5, wear resistance and wet earth-catching property are poor.

On the other hand, in an embodiment, wear resistance and energy-to-break index are good, and embodiment 1 and 2 Fractures can and wear resistance good especially, and particularly in comparative example 1, energy-to-break is very good.In addition, in thering is the embodiment 1 and 2 of following condition: the mixture of alkaline fat acid metal salt, aliphatic carboxylic acid zinc salt and aromatic carboxylic acid zinc salt, C4-16 aliphatic carboxylic acid zinc salt and lipid acid for example stearic total content in good scope, and use dispersed outstanding white rouge, particularly, in the embodiment 1 of the total content in having special good range, rolling resistance index is good.

Silicon-dioxide favorable dispersity or better in an embodiment, and good especially in the embodiment 2 and 3 that uses anti-reversion agent and dispersed outstanding white rouge.The wet earth-catching property of embodiment and dry earth-catching property are all good, and are equal to or higher than comparative example 1.In having mixed the embodiment 6 and 7 of BR, wear resistance is good.In use, have the epoxy natural rubber 2 of high epoxy content and have in the embodiment 7 of BR2 of outstanding physical strength and wear resistance, when keeping breaking tenacity and wear resistance, wet earth-catching property significantly improves.The result of embodiment 1 and comparative example 1 (using conventional silicon-dioxide and conventional silane coupling agent), comparative example 2 (using white rouge and conventional silane coupling agent) and comparative example 4 (silane coupling agent that uses conventional silicon-dioxide and contain sulfydryl) are compared.This relatively in, in embodiment 1, collaborative improved energy-to-break, wear resistance, rolling resistance and wet earth-catching property, and obtained good dry earth-catching property.

[table 2]

Sidewall and rubber composition for base tread

In comparative example 8, the silicon-dioxide of use is not according to white rouge of the present invention, and has used the coupling agent that there is no sulfydryl.Therefore, poor than embodiment of the energy-to-break of comparative example 8, tear strength and warp resistance crack growth resistance.In addition, in comparative example 8, the result of constant elongation fatigue test is poor, and if this rubber combination is used for sidewall and tread base, weather resistance and splitting resistance are not enough so.In comparative example 9, used white rouge but there is no to use the coupling agent that contains sulfydryl.Therefore, in comparative example 9, silicon-dioxide disperses non-constant, and energy-to-break and tear strength are poorer than embodiment's.In addition, the warp resistance crack growth resistance of comparative example 9 is, poor than embodiment of the result of constant elongation fatigue test.Equally, in comparative example 10, used white rouge but there is no to use the coupling agent that contains sulfydryl.Therefore, in comparative example 10, silicon-dioxide disperses non-constant, and energy-to-break, tear strength and warp resistance crack growth resistance be on duty mutually, and also poor than embodiment of the result of constant elongation fatigue test and rolling resistance.

In comparative example 11, the coupling agent that has used conventional silicon-dioxide and contained sulfydryl, so time of scorch is shorter.In addition, because do not use white rouge in comparative example 11, so poor than embodiment of energy-to-break, tear strength and warp resistance crack growth resistance.In addition, in comparative example 11, the result of constant elongation fatigue test is poor, and if this rubber combination is used for sidewall and tread base, weather resistance and splitting resistance are not enough so.In comparative example 12, used conventional silicon-dioxide and be different from the coupling agent that contains sulfydryl in comparative example 11.Therefore, time of scorch is very short, and is difficult to process by common method.In addition, the result of the energy-to-break of comparative example 12, tear strength, warp resistance crack growth resistance, constant elongation fatigue test is poor.

On the contrary, in an embodiment, energy-to-break exponential sum tear strength index is good.Embodiment 8 and 9 Fractures can and tear strength good especially, especially very good in embodiment 8.In addition, in thering is the embodiment 8 and 9 of following condition: mixture, the C of alkaline fat acid metal salt, aliphatic carboxylic acid zinc salt and aromatic carboxylic acid zinc salt _4-16the total content of aliphatic carboxylic acid zinc salt and lipid acid is in good especially scope, and the dispersed outstanding white rouge of use, and rolling resistance index is good.Silicon-dioxide favorable dispersity or better in an embodiment, and good especially in the embodiment 9 and 10 that uses anti-reversion agent and dispersed outstanding white rouge.In addition, the warp resistance crack growth resistance of embodiment and the result of constant elongation fatigue test are all good, and good than comparative example 8.

The result of embodiment 8 and comparative example 8 (using conventional silicon-dioxide and conventional silane coupling agent), comparative example 9 (using white rouge and conventional silane coupling agent) and comparative example 11 (silane coupling agent that uses conventional silicon-dioxide and contain sulfydryl) are compared.This relatively shows, in embodiment 8, works in coordination with the result of having improved energy-to-break, tear strength, rolling resistance, warp resistance crack growth resistance and constant elongation fatigue test.

Claims (5)

1. a rubber composition for tire, it comprises:

The rubber component that contains epoxy natural rubber;

Rubber components based on 100 mass parts, the above and trickle silicon-dioxide below 150 mass parts of 5 mass parts;

And the trickle silicon-dioxide based on 100, the above and silane coupling agent below 20 mass parts of 0.5 mass parts,

Wherein, in the rubber components of 100 quality %, the content of described epoxy natural rubber is more than 15 quality %,

Described silicon-dioxide has the 180m measuring according to ASTM D3765-92 ²cTAB specific surface area more than/g and the 185m measuring according to ASTM D3037-81 ²bET specific surface area more than/g,

And described silane coupling agent comprises sulfydryl.

2. rubber composition for tire as claimed in claim 1, is characterized in that,

Described silicon-dioxide has granule size more than 30nm.

3. rubber composition for tire as claimed in claim 1, is characterized in that,

Described silane coupling agent is the multipolymer that contains unit B shown in unit A shown in general formula (1) and general formula (2), and the ratio of unit B be unit A and unit B total molar content 1 to 70mol%:

Wherein, x and y are respectively more than 1 integers,

R ¹represent hydrogen, halogen, have side chain or unbranched C _1-30alkyl or alkylidene group, there are side chain or unbranched C _2-30thiazolinyl or alkenylene, there are side chain or unbranched C _2-30the hydrogen atom of alkynyl or alkynylene or its alkyl or alkenyl end is by the group of hydroxyl or carboxyl substituted,

R ²represent hydrogen, have side chain or unbranched C _1-30alkyl or alkylidene group, there are side chain or unbranched C _2-30thiazolinyl or alkenylene or have side chain or unbranched C _2-30alkynyl or alkynylene, and

R ¹and R ²can form together ring texture.

4. rubber composition for tire as claimed in claim 1, is characterized in that, described composition is for tyre surface, sidewall or tread base.

5. a pneumatic tyre that uses rubber combination as claimed in claim 1 to produce.